Ultrafast Singlet Energy Transfer before Fission in a Tetracene/WSe2 Type II Hybrid Heterostructure.

Hybrid heterostructures comprising organic and two-dimensional (2D) layered semiconductors hold great promise for light harvesting and optoelectronic applications. Among them, organic materials that exhibit singlet fission (SF) in which one singlet exciton generates two triplet excitons are particularly attractive and can potentially improve the performance of the device. However, SF-enhanced devices require that SF can compete with direct energy/charge transfer from the singlet exciton. Here, we performed ultrafast spectroscopic studies on a prototypical heterostructure consisting of tetracene (Tc) and monolayer WSe2. We show a type II band alignment with 16.5 ps hole transfer from photoexcited WSe2 to tetracene and a long-lived (∼565 ps) charge separation. Importantly, we show ultrafast (∼3.4 ps) singlet exciton energy transfer from photoexcited tetracene to WSe2, prior to the slow SF process (>20 ps) in tetracene. This study raises the challenge and calls for the careful design of SF-enhanced 2D optoelectronic devices.

Momentarily trapped exciton polaron in two-dimensional lead halide perovskites.

Two-dimensional (2D) lead halide perovskites with distinct excitonic feature have shown exciting potential for optoelectronic applications. Compared to their three-dimensional counterparts with large polaron character, how the interplay between long- and short- range exciton-phonon interaction due to polar and soft lattice define the excitons in 2D perovskites is yet to be revealed. Here, we seek to understand the nature of excitons in 2D CsPbBr3 perovskites by static and time-resolved spectroscopy which is further rationalized with Urbach-Martienssen rule. We show quantitatively an intermediate exciton-phonon coupling in 2D CsPbBr3 where exciton polarons are momentarily self-trapped by lattice vibrations. The 0.25 ps ultrafast interconversion between free and self-trapped exciton polaron with a barrier of ~ 34 meV gives rise to intrinsic asymmetric photoluminescence with a low energy tail at room temperature. This study reveals a complex and dynamic picture of exciton polarons in 2D perovskites and emphasizes the importance to regulate exciton-phonon coupling.

Solvent effects on triplet-triplet annihilation upconversion kinetics of perylene with a Bodipy-phenyl-C60 photosensitizer.

The solvent effect usually plays an important role in triplet-triplet annihilation (TTA) upconversion processes. In this work, we have studied the TTA upconversion kinetics of perylene with Bodipy-phenyl-C60 as the triplet photosensitizer in five solvents, 1,4-dioxane, dichlorobenzene, chlorobenzene, toluene, and tetrahydrofuran (THF). Although no significant solvent effect was observed in steady-state absorption and fluorescence emission spectra, the overall TTA upconversion quantum yields showed a profound dependence on solvent properties, i.e. 4.9% in 1,4-dioxane, 7.1% in dichlorobenzene, 6.7% in chlorobenzene, 4.6% in toluene, and 2.2% in THF (the maximum of 50%). Each elementary reaction step involved in the overall process was analyzed by applying femtosecond and nanosecond time-resolved transient absorption spectroscopy, revealing that the fluorescence emission of perylene was more significantly affected by the solvents in contrast to the other steps. Moreover, an extra intramolecular energy-transfer pathway of Bodipy-phenyl-C60 was found via the formation of charge-separated states in dichlorobenzene, chlorobenzene, and THF solvents, once being excited. These conclusions provide valuable clues to choose the most favorable solvent for the higher TTA upconversion efficiency in related applications.

Dynamic polaronic screening for anomalous exciton spin relaxation in two-dimensional lead halide perovskites.

Two-dimensional lead halide perovskites with confined excitons have shown exciting potentials in optoelectronic applications. It is intriguing but unclear how the soft and polar lattice redefines excitons in layered perovskites. Here, we reveal the intrinsic exciton properties by investigating exciton spin dynamics, which provides a sensitive probe to exciton coulomb interactions. Compared to transition metal dichalcogenides with comparable exciton binding energy, we observe orders of magnitude smaller exciton-exciton interaction and, counterintuitively, longer exciton spin lifetime at higher temperature. The anomalous spin dynamics implies that excitons exist as exciton polarons with substantially weakened inter- and intra-excitonic interactions by dynamic polaronic screening. The combination of strong light matter interaction from reduced dielectric screening and weakened inter-/intra-exciton interaction from dynamic polaronic screening explains their exceptional performance and provides new rules for quantum-confined optoelectronic and spintronic systems.

Highly Efficient Multiple Exciton Generation and Harvesting in Few-Layer Black Phosphorus and Heterostructure.

Multiple exciton generation (MEG) in semiconductors that yields two or more excitons by absorbing one high-energy photon has been proposed to break the Shockley-Queisser limit and boost photon-to-electron conversion efficiency. However, MEG performance in conventional bulk semiconductors or later colloidal nanocrystals is far from satisfactory. Here, we report efficient MEG in few-layer black phosphorus (BP), a direct narrow bandgap two-dimensional (2D) semiconductor with layer-tunable properties. MEG performance improves with decreasing layer number and reaches 2.09Eg threshold and 93% efficiency for two-layer BP, approaching energy conservation limit. The enhanced MEG can be attributed to strong Coulomb interaction and high density of states in 2D materials. Furthermore, MEG of BP shows negligible degradation in vertical heterostructure and multielectron can be extracted by interfacial transfer with near unity yield. These results suggest 2D semiconductors as an ideal system for next generation highly efficient light emission and charge transfer devices.

Infrared driven hot electron generation and transfer from non-noble metal plasmonic nanocrystals.

Non-noble metal plasmonic materials, e.g. doped semiconductor nanocrystals, compared to their noble metal counterparts, have shown unique advantages, including broadly tunable plasmon frequency (from visible to infrared) and rich surface chemistry. However, the fate and harvesting of hot electrons from these non-noble metal plasmons have been much less explored. Here we report plasmon driven hot electron generation and transfer from plasmonic metal oxide nanocrystals to surface adsorbed molecules by ultrafast transient absorption spectroscopy. We show unambiguously that under infrared light excitation, hot electron transfers in ultrafast timescale (<50 fs) with an efficiency of 1.4%. The excitation wavelength and fluence dependent study indicates that hot electron transfers right after Landau damping before electron thermalization. We revealed the efficiency-limiting factors and provided improvement strategies. This study paves the way for designing efficient infrared light absorption and photochemical conversion applications based on non-noble metal plasmonic materials.

Controlling Exciton and Valley Dynamics in Two-Dimensional Heterostructures with Atomically Precise Interlayer Proximity.

Two-dimensional (2D) materials and heterostructures with strong excitonic effect and spin/valley properties have emerged as an exciting platform for optoelectronic and spin/valleytronic applications. There, precise control of the exciton transformation process (including intralayer to interlayer exciton transition and recombination) and valley polarization process via structural tuning is crucial but remains largely unexplored. Here, using hexagonal boron nitride (BN) as an intermediate layer, we show the fine-tuning of exciton and valley dynamics in 2D heterostructures with atomic precision. Both interfacial electron and hole transfer rates decrease exponentially with increasing BN thickness, which can be well-described with quantum tunneling model. The increased spatial separation with BN intercalation weakens the electron-hole Coulomb interaction and significantly prolongs the interlayer exciton population and valley polarization lifetimes in van der Waals (vdW) heterostructures. For example, WSe2/WS2 heterostructures with monolayer BN intercalation exhibit a hole valley polarization lifetime of ∼60 ps at room temperature, which is approximately threefold and 3 orders of magnitude longer than that in WSe2/WS2 heterobilayer without BN and WSe2 monolayer, respectively. Considering a large family of layered materials, this study suggests a general approach to tailor and optimize exciton and valley properties in vdW heterostructures with atomic precision.

Photoexcitation-controlled self-recoverable molecular aggregation for flicker phosphorescence.

Chemical systems with external control capability and self-recoverability are promising since they can avoid additional chemical or energy imposition during the working process. However, it remains challenging to employ such a nonequilibrium method for the engineering of optoelectronic function and for visualization. Here, we report a functional molecule that can undergo intense conformational regulation upon photoexcitation. It enables a dynamical change in hydrophobicity and a follow-up molecular aggregation in aqueous media, accordingly leading to an aggregation-induced phosphorescence (AIP) behavior. This successive performance is self-recoverable, allowing a rapid (second-scale cycle) and long-standing (>103 cycles) flicker ability under rhythmical control of the AIP. Compared with traditional bidirectional manipulations, such monodirectional photocontrol with spontaneous reset profoundly enhances the operability while mostly avoiding possible side reactions and fatigue accumulation. Furthermore, this material can serve as a type of luminescent probe for dynamically strengthening visualization in bioimaging.

Application of a bodipy-C70 dyad in triplet-triplet annihilation upconversion of perylene as a metal-free photosensitizer.

A bodipy-C70 dyad was synthesized and applied in triplet-triplet annihilation (TTA) upconversion of perylene as a novel metal-free organic photosensitizer. The photophysical processes were investigated by the methods of steady-state UV-Vis absorption and fluorescence spectroscopy, nanosecond time-resolved transient absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The bodipy-C70 dyad showed an increased molar extinction coefficient up to 82 300 mol-1 cm-1 at 518 nm compared with the C70 monomer. With photo-excitation of the bodipy moiety at 532 nm, the intramolecular singlet-singlet energy transfer between bodipy and C70 units was efficient with a quantum yield of nearly 100%, and the lowest triplet state of the dyad was subsequently populated via ISC of the C70 moiety, with a lifetime of ca. 80 µs in toluene. Electrochemical investigation suggested that the intramolecular electron transfer of the excited dyad was thermodynamically prohibited in toluene due to the positive ΔGCS for charge-separation. With the presence of perylene in solution as the triplet energy acceptor and emitter, the TTA upconverted fluorescence was observed with a maximum quantum yield of 10.3%. The overall upconversion capability of 4417 M-1 cm-1 exceeded that of C70 approximately two-fold. Moreover, the bodipy-C70 dyad also exhibited an enhanced optical stability under intense irradiation. All data indicated that the dyad was another ideal photosensitizer for TTA upconversion of perylene in the fullerene derivative family.

Interference of P-REX2a may inhibit proliferation and reverse the resistance of SGC7901 cells to doxorubicin.

Drug resistance inhibits the efficacy of doxorubicin in gastric cancer. Phosphatidylinositol 3,4,5-trisphosphate RAC exchanger 2a (P-REX2a) activates the phosphatidylinositol-3-kinase (PI3K)/protein kinase B (Akt) signaling pathway by binding to and inactivating phosphatase and tensin homolog (PTEN), which functions as a tumor promoter in a number of types of cancer. However, there is no research concerning the association between P-REX2a expression and drug resistance in gastric cancer. In the present study, the expression of P-REX2a in clinical gastric cancer tissues was detected, and the mechanism of doxorubicin resistance in the gastric cancer cell line SGC7901 was investigated. Using reverse transcription-quantitative polymerase chain reaction and western blotting, it was demonstrated that the mRNA and protein expression of P-REX2a was increased in gastric cancer tissues. MTT assays were also used to determine proliferation, and proliferation was revealed to be reduced following transfection of P-REX2a small interfering (si)RNA. When the cells were treated with 0.3 µM doxorubicin for 24 h, the rate of apoptosis in the siRNA-transfected groups significantly increased and no marked changes in of PTEN and Akt expression were observed. By contrast, the activity of PTEN increased, and the expression of p-Akt (S473) decreased in the P-REX2a siRNA-transfected group compared with the control. The detection of PTEN enzymatic activity in the present study was based on phosphatidylinositol-3,4,5-trisphosphate. Therefore, it was concluded that P-REX2a may participate in the generation of resistance to doxorubicin in gastric cancer, and this may be associated with the upregulation of the PI3K/Akt signaling pathway via inactivation of PTEN.

Photochemical Reaction Between 1,2-Naphthoquinone and Adenine in Binary Water-Acetonitrile Solutions.

The photochemical reaction between 1,2-naphthoquinone (NQ) and adenine was investigated using nanosecond time-resolved laser flash photolysis. With photolysis at 355 nm, the lowest triplet state T1 of NQ was produced via intersystem crossing from its singlet excited state. The triplet-triplet absorption of the state contributes three bands of transient spectra at 374, 596 and 650 nm, respectively, in pure acetonitrile and binary water-acetonitrile solutions. In the presence of adenine, the observation of A·+ (at 363 nm) and NQ+H· radical (at 343 and 485 nm) indicates a multistep mechanism of electron transfer process followed by a proton transfer between 3 NQ* and adenine. By fitting with the Stern-Volmer relationship, the quenching rate constant kq of 3 NQ* by adenine in binary water-acetonitrile solutions (4/1, volume ratio, v/v) is determined as 1.66 × 109  m-1  s-1 . Additionally, no spectral evidence confirms the existence of electron transfer between 3 NQ* with thymine, cytosine and uracil.

Triplet-triplet annihilation upconversion kinetics of C60-Bodipy dyads as organic triplet photosensitizers.

Three new triplet photosensitizers consisting of a bodipy derivative and C60 moieties were synthesized for triplet-triplet annihilation upconversion of perylene. With the extension of the π-conjugated structure of the bodipy derivative, the three photosensitizers exhibited different absorption wavelengths, e.g. 517 nm for B-2, 532 nm for B-4, and 557 nm for B-6. The steady-state and transient absorption, steady-state fluorescence, and upconverted fluorescence emission were investigated to reveal step-by-step the dynamic processes of the above systems. The quantum yields of intramolecular energy transfer, intersystem crossing, and triplet-triplet energy transfer were measured. From the upconverted fluorescence emission spectra, the overall quantum yield of the triplet-triplet annihilation upconversion, ΦUC, was determined to be 5.80% for B-2, 7.95% for B-4, and 4.99% for B-6.

Solvent effects on the triplet-triplet annihilation upconversion of diiodo-Bodipy and perylene.

Solvent effects play a very important role in photochemical reactions and energy transfer processes in solution; however, these effects are rarely mentioned in the triplet-triplet annihilation (TTA) upconversion fluorescence experiments. In a typical TTA upconversion system of a photosensitizer of diiodo-Bodipy (I2-Bodipy) and a triplet acceptor of perylene, five common inert solvents, hexane, heptane, toluene, 1,4-dioxane, and dimethyl sulfoxide (DMSO), were used to investigate the solvent effects on the overall quantum yield of upconversion fluorescence. Femtosecond and nanosecond time-resolved transient difference absorption spectra were obtained to study the efficiencies of intersystem crossing (ISC) and triplet-triplet energy transfer (TTET). From the obtained upconversion fluorescence emission spectra, the overall TTA upconversion fluorescence quantum yield was derived. Among the five solvents, the upconversion quantum yield in dioxane is the highest at 19.16%, more than twice that that in toluene (8.75%). For the solvents hexane, heptane, toluene, and dioxane, the yields generally follow the sequences of polarity and viscosity. However, a very low upconversion quantum yield (1.51%) was observed in DMSO although the TTET process and fluorescence quantum yield of perylene in DMSO were almost as efficient as in dioxane. Based on density functional theory calculations, a reasonable explanation for these solvent effects was proposed.

Diagnostic accuracy of the 14C-urea breath test in Helicobacter pylori infections: a meta-analysis.

OBJECTIVES: To summarize and appraise the available literature regarding the use of the 14C-urea breath test in the diagnosis of Helicobacter pylori infections in adult patients with dyspepsia and to calculate pooled diagnostic accuracy measures. METHODS: We systematically searched the PubMed, EMBASE, Cochrane Library, Chinese Journals Full-text (CNKI) and CBMDisc databases to identify published data regarding the sensitivity, specificity, and other measures of diagnostic accuracy of the 14C-urea breath test in the diagnosis of Helicobacter pylori infections in adult patients with dyspeptic symptoms. Risk of bias was assessed using the QUADAS (Quality Assessment of Diagnostic Accuracy Studies)-2 tool. Statistical analyses were performed using Meta-Disc 1.4 software and STATA. RESULTS: Eighteen studies met the inclusion criteria. Pooled results indicated that the 14C-urea breath test showed a diagnostic sensitivity of 0.96 (95% CI 0.95 to 0.96) and specificity of 0.93 (95% CI 0.91 to 0.94). The positive like ratio (PLR) was 12.27 (95% CI 8.17 to 18.44), the negative like ratio (NLR) was 0.05 (95% CI 0.04 to 0.07), and the area under the curve was 0.985. The DOR was 294.95 (95% CI 178.37 to 487.70). The 14C-urea breath test showed sufficient sensitivity and specificity for diagnosing Helicobacter pylori infection, but unexplained heterogeneity after meta-regression and several subgroup analyses remained. CONCLUSIONS: The UBT has high accuracy for diagnosing H. pylori infections in adult patients with dyspepsia. However, the reliability of these diagnostic meta-analytic estimates is limited by significant heterogeneity due to unknown factors.